This invention relates to new binders for particulate solids, and to the formation of new compacted products formed by use of such binders. In one of its embodiments this invention relates to novel 1,3-dihalo-5,5-dimethylhydantoin compositions which, by virtue of their physical forms and characteristics, are superlative biocidal water-treating agents and brominating agents.
As used herein the terms xe2x80x9chalogenxe2x80x9d, xe2x80x9chalogenatedxe2x80x9d, and xe2x80x9chaloxe2x80x9d are with reference to bromine or chlorine, or both.
As is well known, a wide variety of different products in the form of powders or small particles are converted into larger end use forms such as prills, flakes, granules, pills, caplets, tablets, wafers, briquettes, pucks, and the like. In producing such products, it is common to utilize materials known as binders. Such materials, when mixed in suitable proportions with the powder or small particles to be compacted, facilitate the production of materials having desirable physical and mechanical properties. While some binders have relatively broad application to various powdery or small particle sized products, there are a number of instances where the binder can only be used for compaction of certain products and not for others. A principal reason for such limitation is chemical incompatibility as between the binder and certain powdery or small particle sized materials. A second reason for such limitation relates to the property of certain binders to modify the solubility characteristics of the powdery or finely-divided substrate material. For example, some binders are chosen not only for their ability to facilitate compaction, but to enable more rapid disintegration of the compacted form of the material, e.g., for more rapid uptake of a pharmaceutical by a consumer.
One type of material that tends to be difficult to produce in compacted forms such as tablets, granules, and briquettes is halogenated hydantoins, especially N,Nxe2x80x2-dihalogenated dialkylhyantoin products such as 1,3-dichloro-5,5-dimethylhydantoin, N,Nxe2x80x2-bromochloro-5,5-dimethylhydantoin, and 1,3-dibromo-5,5-dimethylhydantoin. Such materials are useful as biocides for treating water such as recreational water, cooling water, process water, and wastewater.
The N,Nxe2x80x2-dihalogenated dialkylhydantoin products are usually formed as powdery solids. For use in many applications such as water treatment, the dry powders need to be converted into larger forms such as granules, tablets, or briquettes. This in turn has presented problems associated with providing densified or compacted products with sufficient strength to withstand the physical stresses encountered in packaging, conveying, handling, shipping, storage, and use. The nature of these problems have been described, for example, in U.S. Pat. Nos. 4,532,330; 4,560,766; 4,654,424; 4,677,130; 4,745,189; and 5,565,576. The approaches described in these patents for alleviating one or more such problems involve use of other materials. Thus in U.S. Pat. Nos. 4,532,330 and 4,621,096, halogenated dimethylhydantoins are mixed with calcium chloride and water, and the mixture is compacted by compression into the desired shape. In U.S. Pat. Nos. 4,560,766 and 4,654,424, halogenated ethylhydantoins are used instead of halogenated dimethylhydantoins and are compacted as such, or are melt blended with halogenated dimethylhydantoins. U.S. Pat. No. 4,677,130 describes forming dry blends of the halogenated dimethylhydantoin with particulate alkali metal or alkaline earth metal salt followed by compression to form a compacted product such as a tablet.
Manufacturers of halogenated hydantoins have sought to overcome these limitations by blending the materials with process additives designed to improve compaction characteristics. The presence of other halogenated hydantoins has also been indicated to provide benefits. For example, published PCT Application WO 97/43264 describes the use of 1,3-bromochloro-5-methyl-5-propylhydantoin as a binder in making compacted forms of halogenated hydantoins. The presence of hydantoins having at least one ethyl group in the 5-position is indicated to provide free flowing, dust-free powders which can be compressed into shapes without resorting to binders, as detailed in U.S. Pat. Nos. 4,427,692 and 4,560,766. In U.S. Pat. No. 4,677,130 a series of inorganic salt additives ranging from sodium carbonate to sodium metasilicate was indicated to improve the crush strength of halogenated hydantoin tablets. Inert binders such as fatty acid salts and a hectorite clay were advocated in U.S. Pat. No. 5,756,440, while the use of fatty acid amide binder additives were described in U.S. Pat. No. 5,565,576 and indicated to improve the compaction properties of halogenated hydantoins. U.S. Pat. No. 5,780,641 describes a chemical composition comprising a halogenated hydantoin mixed with dry calcium hydroxide for the purpose of facilitating processing and achieving a shape-retentive form.
Unfortunately, almost all prior efforts in the compaction of halogenated hydantoins have not provided binders having satisfactory compaction characteristics along with good chemical compatibility. Some of the classical binders (e.g., polyvinylpyrrolidinone, cellulose compounds, glues, gums, sugars, and starches) which are used to compact other products would react with halogenated hydantoins, in some cases vigorously. Moreover, a number of binder systems proposed for use with halogenated hydantoins do not provide compacted products having sufficient physical and mechanical stability. Low crush strength is often another deficiency of such compacted products.
In addition to having a binder suitable for use with a wide variety of materials, and capable of producing compacted products having desirable physical and mechanical properties, it would be of considerable advantage if such binder could be employed with materials suitable for human consumption.
It can be seen that a need exists for a new type of binder having widespread applicability to powdery and finely-divided substrate materials, especially halogenated hydantoins. It would be of particular advantage if such binders could provide compacted products having superior physical and mechanical properties. Moreover, it would be of inestimable value if the binder having these characteristics could itself be suitable for consumption by humans and animals.
This invention is deemed to fulfill most, if not all, of the foregoing needs.
Pursuant to this invention, a new type of binding agent for powdery or finely-divided materials has been discovered. These binders produce compacted compositions of great mechanical and physical strength. This highly beneficial result can be achieved with a wide variety of such materials inasmuch as these binders have good compatibility with a wide range of powdery or finely-divided materials. Moreover, the binders used pursuant to this invention are suitable for ingestion by humans and animals. Furthermore, these binders are strongly hydrophobic, and consequently can be used for modifying the dissolution or release rate of the compacted material in aqueous media. Also, because they are produced and used for other purposes, a number of the materials discovered to be binders pursuant to this invention are available in the marketplace at reasonable cost. Thus, the invention enables the production of compacted compositions such as granules, caplets, tablets, briquettes, pucks, and other shapes with very desirable properties on a highly cost-effective basis.
Thus, in one of its embodiments, this invention provides a shape-retentive compacted composition. The composition comprises a pressure compacted blend of a powdery or finely-divided active ingredient and a binder quantity of a micronized synthetic polyolefin-based hydrocarbon wax and/or a micronized synthetic polyfluorocarbon wax. The wax used pursuant to this invention is compatible with the active ingredient.
In particular, prior small particle sized product, when released from a tableting die, normally would xe2x80x9cdelaminatexe2x80x9d, meaning that the compacted tablet would break apart into smaller pieces. In sharp contrast, 1,3-dihalo-5,5-dimethylhydantoins, especially 1,3-dibromo-5,5-dimethylhydantoin, can be directly converted into tablets of high physical integrity when using a suitable micronized wax as a binder.
In another of its embodiments, this invention provides a method of producing a shape-retentive compacted composition. The method comprises pressure compacting a blend of a powdery or finely-divided active ingredient and a binder quantity of a micronized synthetic polyolefin-based hydrocarbon wax and/or a micronized synthetic polyfluorocarbon wax. Here again, the wax used is compatible with the active ingredient.
Still another embodiment of this invention involves the provision of dry blends of a powdery or finely-divided active ingredient and a micronized synthetic polyolefin-based hydrocarbon wax and/or a micronized synthetic polyfluorocarbon wax, compatible with the active ingredient. These blends are of particular utility in the manufacture of pressure compacted products formed therefrom. Thus, these dry blends can be produced, stored, and shipped to locations where such compacting operations are to be carried out. Preferably, the amount of the micronized synthetic polyolefin-based hydrocarbon wax and/or a micronized synthetic polyfluorocarbon wax is an amount which is effective to form the compacted product without further addition of either component. However, the proportions can be adjusted at the site of the compaction, if desired.
The amount of the binding agent effective to form the compacted product may vary, depending upon the nature and characteristics of the active ingredient and the particular micronized wax being utilized. Thus the dry blends and the compacted products of this invention can contain varying proportions of these essential components. Generally speaking, the amount of the micronized wax in the dry blends and used in the formation of the pressure compacted products of this invention will fall within the range of about 0.5 to about 10 wt %, and preferably in the range of about 1 to about 5 wt %, based on the total weight of the active ingredient and the micronized wax.
In preferred embodiments, the powdery or finely-divided material is an N-halo-5,5-dialkylhydantoin or, more preferably, an N,Nxe2x80x2-dihalo-5,5-dialkylhydantoin, materials which heretofore have proven exceedingly difficult to convert into compacted forms. Moreover, even when compacted, such prior compacted forms of the N,Nxe2x80x2-dihalo-5,5-dialkylhydantoins were, in most cases, of low strength and of high friability. It has been discovered that when low levels of the aforementioned waxes are mixed with a halogenated hydantoin, the wax acts as binder during pressure compaction to yield a mechanically stable compacted form of increased strength and of low friability. Furthermore, it has been discovered that the waxes are chemically compatible with the halogenated hydantoin.
A feature of this invention is that it is now possible to formulate blends of one or more halogenated hydantoins with one or more novel binders so that compacted products having improved physical and mechanical properties can be produced. Additionally, adjustment of the amount of binder permits adjustments in the rate of dissolution of the active ingredient. In short, the dissolution characteristics of the product can be tailor-made to suit the needs of the intended usage of the product. For example, it is possible to produce a compacted form with slow dissolution properties that would be desirable in a toilet bowl puck or in a swimming pool formulation. Similarly, products with much more rapid dissolution characteristics can be prepared for use in shock treatment of water for microbiological control.
Another feature is that by use of the micronized wax binders, compacted products of this invention with crush strengths in the range of from about 60 to about 200 pounds per inch of thickness can be formed. Thus, these compacted products are capable of withstanding, to a greater extent, the physical stresses encountered in packaging, conveying, handling, shipping, storage, and use.
Other embodiments, features, and advantages of this invention will become still further apparent from the ensuing description and appended claims.
The exact mechanism by which the micronized waxes perform the function of producing durable pressure compacted shapes or forms from powdery, finely-divided solids is not known. Without in any way being limited by theory, it may be that the micronized wax serves in whole or in part as an adhesive or bonding agent, for example by forming, when under the compaction pressure, a film between adjacent particles that bonds the particles together and thus acts like a pressure-activated cement. It is also possible that the micronized wax serves in whole or in part as a lubricant which, by reducing the coefficient of friction among adjacent particles, enables the particles to come in closer contact with each other during application of compression pressure so that large numbers of inter-particulate bonding or fusion sites are created among the adjacent particles. It is also possible that the micronized wax enables the particles to be more readily distorted under compression pressure so that the particles can more completely bond or fuse together while under such pressure. Indeed, combinations of these and/or other mechanisms may be taking place during the application of the compression pressure to a mixture of the particulate substrate and the micronized wax.
Therefore it cannot be over-emphasized that this invention is not intended to be limited, should not be interpreted as being limited, and is not to be limited in any way to any mechanism or theory of operation. Thus, for example, while the term xe2x80x9cbinderxe2x80x9d is used herein with reference to the micronized wax, such term is not intended to limit this invention to any mechanism, theory, or mode of operation; should not be interpreted as limiting this invention to any mechanism, theory, or mode of operation; and does not limit this invention in any way to any mechanism, theory or mode of operation. Rather the term is used to indicate that the micronized wax somehow or other functions such that when the compression pressure is released, the particles have come together into a durable form or shape that not only can be released from the mold or nip of the compression rolls without physical damage, but that possess the strength and durability to withstand the physical stresses encountered in packaging, conveying, handling, shipping, storage, and use of the compacted article. Exactly how this result actually comes about in a mechanistic or theoretical sense is immaterial to the practice of this invention. The point is: the invention works. How it works matters not.
Various micronized waxes cam be used in the practice of this invention. As noted above, these micronized waxes are typically micronized polyolefin waxes, or micronized polyfluorocarbon waxes, or mixtures thereof. While the average particle size of the wax can vary within reasonable limits, preferred micronized waxes typically have, prior to compaction, an average particle size of no greater than about 15 microns. Similarly, preferred micronized waxes typically have, prior to compaction, a maximum particle size of no greater than about 40 microns. In most cases, the micronized wax has, prior to compaction, a bulk density in the range of about 0.9 to about 1.4 grams per cc at 25xc2x0 C. Another characteristic of preferred micronized waxes is that they at least partially melt at a temperature in the range of about 100xc2x0 C. to about 150xc2x0 C.
Among particularly preferred micronized polyethylene waxes are those which, prior to compaction, (a) melt at a temperature in the range of about 109xc2x0 C. to about 111xc2x0 C., or (b) have an average particle size in the range of about 6.0 to about 8.0 microns, or (c) a maximum particle size of about 22 microns, or (d) have a combination of any two or all three of (a), (b), and (c).
Included among particularly preferred polypropylene waxes, are those materials which are characterized, prior to compaction, by having (a) a melting temperature in the range of about 140xc2x0 C. to about 143xc2x0 C., or (b) an average particle size in the range of about 5.0 to about 7.0 microns, or (c) a maximum particle size of about 22 microns, or a combination of any two or all three of (a), (b), and (c).
Particularly preferred micronized wax blends include micronized polyolefin and polyfluorocarbon wax blends which, prior to compaction, at least partially melt at a temperature in the range of about 104xc2x0 C. to about 126xc2x0 C. Among these blends are those which, prior to compaction, (a) partially melt at a temperature in the range of about 104xc2x0 C. to about 110xc2x0 C., or (b) have an average particle size in the range of about 5 to about 7 microns, or (c) have a maximum particle size of about 22 microns, or (d) have a combination of any two or all three of (a), (b), and (c). Also included among these blends are those which, prior to compaction, (a) partially melt at a temperature in the range of about 124xc2x0 C. to about 126xc2x0 C., or (b) have an average particle size in the range of about 9 to about 11 microns, or (c) have a maximum particle size of about 31 microns, or (d) have a combination of any two or all three of (a), (b), and (c).
Other particularly preferred micronized waxes are modified polyfluorocarbon waxes which, prior to compaction, (a) partially melt at a temperature in the range of about 108xc2x0 C. to about 115xc2x0 C., or (b) have an average particle size in the range of about 5 to about 6 microns, or (c) have a maximum particle size of about 22 microns, or (d) have a combination of any two or all three of (a), (b), and (c).
Various methods can be used in forming the dry blends of this invention. Among preferred methods are use of ribbon blenders or tumble blenders for mixing the active ingredient and the micronized wax. Equipment of this type is readily available in the marketplace from a number of reputable suppliers. As noted above, the amount of the micronized wax in the dry blends of this invention will fall within the range of about 0.5 to about 10 wt %, and preferably in the range of about 1 to about 5 wt %, based on the total weight of the active ingredient and the micronized wax. It will be understood and appreciated that departures from these ranges are permissible without departing from the scope of this invention, whenever such departures are deemed necessary or appropriate.
Numerous active ingredients can be utilized in forming the dry blends and the compacted products of this invention. Included among such active ingredients are, for example, pharmaceuticals, dietary supplements, agricultural chemicals, animal feeds, water treating agents, biocidal agents, polymer additives, pesticides, and similar substances which are normally in the solid state of aggregation. In the blending and compaction of such active ingredients, additional components can be included in order to partake of their desirable functions and characteristics. Such additional components, often termed excipients, include lubricants, disintegrants, and mold release agents. Other optional ingredients which may be used in the formulation of products include fragrances, stabilizers, adjuvants, corrosion inhibitors, dyes, surfactants, synergists, effervescents, diluents, builders, chelating agents, buffers, and the like. Such ancillary materials should of course be compatible with the active ingredient and not interfere in any material way with its performance characteristics.
Another feature of this invention is that certain powdery or finely-divided active ingredients, when blended with a suitable micronized wax, can be converted directly into pressure compacted forms, such as caplets or tablets.
One preferred group of active ingredients for use in the practice of this invention are the finely-divided or powdery profen pharmaceuticals, such as, for example, ibuprofen, ketoprofen, naproxen, pirprofen, carprofen, flurbiprofen, and similar non-steroidal analgesics of this general type.
Another preferred group of active ingredients used in the practice of this invention is comprised of 1,3-dihalo-5,5-dialkylhydantoins, especially 1,3-dibromo-5,5-dimethylhydantoin, 1,3-dichloro-5,5-dimethylhydantoin, 1-bromo-3-chloro-5,5-dimethylhydantoin, and 1-chloro-3-bromo-5,5-dimethylhydantoin, or mixtures of two or more of them. These are biocidal agents for use in water treatment. These compounds are, in general, sparingly soluble in water. Thus typically for water treatment applications 1,3-dichloro-5,5-dimethylhydantoin is supplied in the form of a puck for insertion into a toilet tank. These pucks apparently are formed by use of one or more binders, such as 1,3-dichloro-5-ethyl-5-methylhydantoin and/or ethylenebis(stearamide). N,Nxe2x80x2-bromochloro-5,5-dimethylhydantoin is supplied in solid forms such as granules, tablets, or briquettes for delivery into the water being treated by means of water flow through an erosion feeder, or in the form of pucks for insertion into a toilet tank. Here again, these solid forms apparently are produced by use of one or more binders such as 1,3-dichloro-5-ethyl-5-methylhydantoin and/or ethylenebis(stearamide).
In converting the 1,3-dihalo-5,5-dimethylhydantoin/binder blends of this invention into granules, conventional processing equipment can be used under the usual operating conditions. Typically, the 1,3-dihalo-5,5-dimethylhydantoin/binder blend is compressed into sheet form by means of a roll compactor. This sheet in turn is broken up into small granules by a mechanical device, such as a Chilsonator(copyright) breaker (The Fitzpatrick Company, Elmhurst, Ill.). The granules are then classified by screening into the desired size range. Undersized granules are typically recycled to the roll compactor, whereas oversized granules are recycled to the breaker device.
Average particle size and particle size distribution of the powdery or finely-divided substrate ingredient(s) can vary widely. The only true limitation is that the ingredient(s) being compacted with the micronized wax are not so large or of such character that despite the application of the compression pressure and the presence of the micronized wax, such ingredient(s) are incapable of being compacted and bound together into a durable form or shape. Typically this invention can be used successfully to form durable compacted articles from submicron-sized powders up to granules as large as about 3 U.S. standard mesh size. However, preferably the substrate ingredient(s), such as for example one or more 1,3-dihalo-5,5-dialkylhydantoins, and especially 1,3-dibromo-5,5-dimethylbydantoin, being shaped or formed pursuant to this invention will have particles with a particle size in the range of from about 20 microns up to about 3 U.S. Standard mesh size. Typically the average particle size of such 1,3-dihalo-5,5-dialkylhydantoins will be in the range of about 20 to about 600 microns. Preferred for use with a binder of this invention is 1,3-dibromo-5,5-dimethylhydantoin particulate solids having an average particle size in the range of about 175 to about 400 microns. Nevertheless departures from these sizes are permissible whenever deemed desirable or appropriate, and thus are within the scope of this invention.
The formation of tablets and other compressed shapes such as briquettes from the blends of this invention can utilize conventionally known processing equipment and, for the most part, known procedures. However, in conducting compaction of the blends of this invention, it is important that the compaction pressure be sufficient to induce plastic deformation and interparticulate binding of the particles. At the same time, the compaction pressure should not be so great as to produce a compacted product which delaminates. Typically, suitable compaction pressures in the practice of this invention will fall within the range of about 1000 to about 30,000 psi, and preferably in the range of about 5000 to about 25,000 psi. Such compaction can be conducted using, for example, a rotary tableting press operated at conventional rotational speeds. Another method for accomplishing the compaction is by means of pressure extrusion through a die orifice, while concurrently shearing the extrudate to produce compacted shapes of the desired size. In such operations, the compaction pressures within the die should be sufficient to induce plastic deformation and interparticulate binding of the particles, but insufficient to produce a compacted product which, when extruded, undergoes an elastic recovery of a magnitude that causes delamination of the compacted extrudate.
When carrying out compaction of a blend of this invention, it is desirable, but not essential, to apply a pressure agglomeration lubricant to the compaction surfaces of the tooling so as to reduce the coefficient of friction between the material being compacted and the tooling. When using such lubricant, it is possible to utilize any of a variety of lubricants conventionally used for this purpose. However, a feature of this invention is that it is highly advantageous to employ, as such lubricant, a micronized wax of the type described herein. Not only is the wax a highly effective lubricant, but in addition, the resultant compacted product is free from contamination by an additional component, namely a lubricant different from the micronized wax.
In operations conducted on a small scale using manually filled dies, 1,3-dibromo-5,5-dimethylhydantoin/binder blends of this invention have been successfully compacted directly into tablets. The tablets when released from the dies were intact and exhibited no visual surface imperfections.
When converted into tablets, briquettes, pucks, and other compacted shapes, the blends of this invention result in compacted forms of greater crush strength.
Granules, tablets, and briquettes produced from 1,3-dihalo-5,5-dimethylhydantoins of this invention are of particular utility as biocidal agents used for treating swimming pools, spas, toilet bowl cleaners, cooling towers, air washer systems, waste water, pulp and paper processing operations, oil field applications, and decorative fountains. Procedures utilizing such articles as biocides in the treatment of water are more fully described in commonly-owned co-pending application Ser. No. 09/484,938, filed Jan. 18, 2000.
As also described above, this invention provides products in which one or more of the 1,3-dihalo-5,5-dimethylhydantoins blends of this invention are converted into granules, caplets, tablets, briquettes, pucks, or any other large size product, however produced. Typical operations of this type have been described above.
While there are no hard and fast rules governing differentiation with respect to size among granules, caplets, tablets, briquettes, and pucks, typically granules are regarded as being particles ranging in size from about 80 to about 3 U.S. standard mesh size. Caplets generally are in the range of about 0.5 to about 1 inch in length and with a cross-sectional width in the range of about 0.25 to about 0.5 inch. Tablets typically fall in the range of from about 0.5 to about 1.0 inch in diameter and about 0.5 to about 1.0 inch in thickness. Briquettes will normally range in size from about 0.5 to about 4.0 inches in length, from about 0.5 to about 4.0 inches in width, and from about 0.5 to about 2.5 inches in height. Pucks are normally disc-shaped objects having a diameter up to about 3.0 inches and a thickness in the range of about 0.5 to about 1.0 inch. It will be understood and appreciated however, that these dimensions are not intended to unduly limit the scope of this invention.
Moreover, when compacted with a suitable binder of this invention, granules, tablets, briquettes, or other relatively small shapes formed from the 1,3-dihalo-5,5-dimethylhydantoins of this invention have excellent physical properties for use in water-treatment systems. The shapes erode at slow, but essentially constant rates when maintained in a constant flow of water. They withstand the customary physical stresses encountered in packaging, conveying, handling, shipping, storage, and use. The compacted solid forms of this invention produced directly from the 1,3-dihalo-5,5-dimethylhydantoin/micronized wax blends have excellent crush strength. In fact, such solid forms can be produced as even larger non-friable shaped articles such as toilet bowl and swimming pool pucks.